Detergent compositions



Oct. 10, 1967 K. w. HERRMANN 3,345,504

DETERGENT COMPOSITIONS Filed March 25, 1966 2 Sheets-Sheet. 1

Temperature Melting Tw Point Surfactant in Water Fig. I

Surfactant 2 nd Isotropic Solution Lye Electrolyte Fig. 2

Kenneth W. Herrmann INVENTOiR.

WCwiiu ATTORNEY Oct. 10, 1967 K. w. HERRM ANN 3 DETERGENT COMPOSITIONSFiled March 25, 1966 r 2 Sheets-Sheet 2 Mesomorphic Phase (Middle orNeat) Surfactant Electrolyte Crystals Solubillzing Electrolyte Fig. 3

Kenneth W. Herrmunn INVENTOR.

BYW

ATTORNEY United States Patent 3,346,504 DETERGENT COMPOSITIONS KennethW. Herrrnann, Greenhills, Ohio, assignor to The Procter & GambleCompany, Cincinnati, Ohio, a corporation of Ohio Filed Mar. 25, 1966,Ser. No. 547,117 11 Claims. (Cl. 252137) This application is acontinuation-in-part of copending application Ser. No. 421,141, nowabandoned, filed Dec. 14, 1964, which is a continuation-in-part ofcopending applications Ser. No. 291,528, filed June 28, 1963, nowabandoned, and Ser. No. 216,119, filed Aug. 10, 1962, now abandoned.

This invention relates to liquid detergent compositions. Specificallythis invention relates to liquid detergent compositions containingcertain detergent surfactants and certain solubilizing electrolytes.

The formulation of liquid detergent compositions is very complex.Ordinarily, it is desirable to keep inert ingredients at a minimum andyet it often becomes necessary to add some compound to the formula whichhas no active detergent effect or detergency builder effect merely tomake the active ingredients compatible with each other and therebycreate a homogeneous composition (i.e., a composition in which there isno bulk separation of a phase). It would therefore be desirable toprovide, in liquid detergent compositions, effective, low costsolubilizing agents and solvents.

Accordingly, it is an object of this invention to provide homogeneousliquid detergent compositions.

It is a further and more specific object of this invention to providesuch compositions containing solubilizing electrolytes and certainspecific detergents.

The aqueous homogeneous liquid detergent compositions of this inventionwhich achieve these objects comprise:

(I) From about 1% to about 40% by weight of the composition of adetergent selected from the group consisting of (A) A detergent havingthe formula (sultaine detergent) wherein R and R are each selected fromthe group consisting of hydrogen, methyl, and ethyl groups, R is astraight chain alkylene group containing from two to four carbon atoms,and having from 0 to one hydroxyl group substituted on a secondarycarbon, and R is an alkyl chain of from about 10 to about 20 carbonatoms;

(B) A detergent having the formula R R R N O (amine oxide detergent)wherein R is selected from the group consisting of alkyl,alkylmonohydroxy, and alkoxy monohydroxypropyl radicals wherein thealkyl and alkoxy portions of said radicals contain from about to about20 carbon atoms and R and R are each selected from the group consistingof alkyl radicals and alkanol radicals containing from one to aboutthree carbon atoms;

(C) A detergent having the formula R' R R P O (phosphine oxidedetergent) wherein R is selected from the group consisting of alkyl, andalkyl monohydroxy radicals containing from about 8 to about 16 carbonatoms and R and R are each selected from the group consisting of alkylradicals and alkanol radicals containing from one to about three carbonatoms;

(D) Nonionic detergents produced by condensing ethylene oxide on ahydrophobic base, e.g., a detergent havr 3,346,504 Patented Oct. 10,1967 ing the formula R (C I-I O),,H (nonionic detergent) wherein Rrepresents a hydrophobic base and preferably is selected from the groupconsisting of (1) alkoxy groups containing from about 8 to about 20carbon atoms, (2) alkyl phenoxy groups (including dialkyl phenoxygroups) wherein the alkyl group contains from about 6 to about 18 carbonatoms, (3) condensation products of propylene glycol and propylene oxidewith a molecular weight of from about 1500 to about 1800, (4) fattyamides containing from about 10 to about 20- carbon atoms, (5) higheralkyl mercaptans containing from about 10 to about 20 carbon atoms, (6)condensation products of propylene oxide and ethylene diamineconstituting from about 20% to about 60% by weight of the finishednonionic detergent molecule and (7) condensation products of fattyalcohols containing from about 10 to about 20 carbon atoms and fromabout three to about 8 propylene oxide units, and wherein x is aninteger from about 4 to about 30 for (1), (2), (4) and (5), but not lessthan about 0.4 of the number of carbon atoms in the hydrophobic base,and sufiiciently large to give the detergent a molecular weight of fromabout 2,000 to about 10,000 for (3), of from about 5,000 to about 11,000for (6) and of from about 750 to about 1800 for (7) and wherein y is aninteger equal to the number of ethylene oxide chains;

(E) A detergent having the formula (sulfoxide detergent) wherein R is analkyl radical containing from about 10 to about 20 carbon atoms andcontains from 0 to 1 hydroxyl substituents, and from 0 to five etherlinkages;

(II) From 0% to about 40% by weight of the composition of a polyvalentelectrolyte salt selected from the group consisting of sulfates;carbonates; pyrophosphates; phosphates; hexametaphosphates;ethylenediaminetetraacetates;N-(Z-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates;N-(2-hydroxyethyl)-nitrilodiacetates; phytates; ethane-l-hydroxy 1,1diphosphonates; methylene diphosphonates; ethylidene, isopropylidene,benzylmethylidene and chloromethylidene diphosphonates; salts ofpolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid,fumaric acid, methylene malonic acid and citraconic acid and copolymerswith themselves and ethylene; and mixtures thereof, the cations of theabove polyvalent electrolytes being selected from the group consistingof sodium, potassium, ammonium, triethanol ammonium, diethanol ammoniumand monoethanol ammonium cations and mixtures thereof;

(III) From about 0.5% to about 20% by weight of the composition andsufficient to keep the composition homogeneous of solubilizingelectrolytes having the formula wherein M is a water soluble cation(e.g., sodium, potassium, ammonium, and alkanolammonium cations) and Ris selected from the group consisting of unsaturated aliphatic radicalscontaining from about 2 to about 7 .carbon atoms; aromatic, substitutedaromatic, and aroelected from the group consisting of chloro, fluoro,and iitro groups and mixtures thereof; and phenyl alkyl 'adicals whereinthe above phenyl radicals are attached alkylene radicals selected fromthe group consisting )f ethylene, propylene, butylene, pentylene, andhexylene groups; branched chain saturated aliphatic radicals conainingfrom about three to about six carbon atoms; and :hloro-substitutedsaturated and unsaturated aliphatic radicals containing from one toabout carbon atoms; and

(IV) The balance substantially water, the composition Jeingsubstantially non-homogeneous when only Components I, II, and IV arepresent, the amount of Component [1 being no more than can be dissolvedin the composition.

The solubilizing electrolyte, Component III, makes homogeneous thoseaqueous mixtures of Component 1, surfactant, and any polyvalentelectrolyte, e.g., builder, present which otherwise would benonhomogenous due to the presence of a bulk, separated phase, e.g., acrystalline phase, or a second immiscible isotropic liquid phase ashereinafter more fully described.

FIGURE 1 is a representative phase diagram for the sultaine detergentsutilized in the compositions of this invention as hereinafter more fullydiscussed.

FIGURE 2 is a representative phase diagram for a detergent of thecompositions of this invention and a typical detergency builderelectrolyte at about room temperature (80 F).

FIGURE 3 is a representative phase diagram for a detergent of thecompositions of this invention and a solubilizing electrolyte of thecompositions of this invention at about room temperature (80 F.).

The first group (A) of the specific detergents, as hereinbeforedescribed, will be referred tohereinafter as sultaines or sultainedetergents. These sultaines are solubilized, according to the instantinvention, in an aqueous solution by the solubilizing electrolyteshereinbefore named. Sultaines of particular interest are those in whichthe long alkyl chain (R) is a mixture of alkyl chains derived fromnaturally occurring substances, whether hydrogenated or not, and theshort alkyl chains are methyl groups. For instance, where R is derivedfrom tallow or coconut oil, R contains three carbon atoms with ahydroxyl group substituted on the middle carbon atom, and R and R aremethyl groups, the sultaines are of particular interest since they arereadily prepared.

Specific examples of the above sultaines include 3-(N,N-dimethyl-N-hexadecyl ammonio)-propane-1-sulfonate,3-(N-hexadecyiammonio)-propane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecyl ammonio -2-hydroxypropane-1- sulfonate. Otherspecific examples include the corresponding decyl, dodecyl, tetradecyl,and octadecyl homologs of the above compounds.

Of special interest as regards the solubilizing electrolytes of thisinvention are relatively water-insoluble sultaines wherein R is an alkylchain of (1) from about 12 to about 18 carbon atoms when R and R arehydrogens, (2) from about 16 to about 20 carbon atoms when R R and Rcontain no substituents, and (3) from about 14 to about 18 carbon atomswhen R and R are alkyl chains, and R is a three carbon atom alkylenegroup with a hydroxyl group substituted on the middle carbon atom. Thesolubilizing electrolytes of this invention solubilize the crystallinephase of these sultaines as hereinafter described.

All the detergents of this invention normally contain mixtures of longalkyl chains (R, R R R and R These can be derived from naturallyoccurring substances such as tallow and coconut oil, and can also bederived from petroleum fractions, e.g., by polymerizing propylene orcracking waxes to form the proper chain length, e.g., in the form of anolefin. The method of deriving the alkyl chain is immaterial. The alkylchains can be unsaturated.

Specific examples of amines oxided detergents include:

dimethyldodecylamine oxide dimethyltetradecylamine oxideethylmethyltetradecylamine oxide cetyldimethylamine oxidedimethylstearylamine oxide cetylethylpropyla-mine oxidediethyldodecylamine oxide diethyltetradecylamine oxidedipropyldodecylamine oxide bis- 2-hydroxyethyl) dodeeylamine oxidebis-(2-hydroxyethyD-3-dodecoxy-1-hydroxypropylamine oxide(2-hydnoxyprOpyDmethyItetradecyIamine oxide dimethyloleylarnine oxidedimethyl- (Z-hydroxydodecyl) amine oxide and the corresponding decyl,hexadecyl, and octadecyl homologs of the above compounds.

Specific examples of the phosphine oxide detergents include:

dimethyldodecylphosphine oxide dimethyltetradecylphosphine oxideethylmethyltetradecylphosphine oxide cetyldimethylphosphine oxidedimethylstearylphosphine oxide cetylethylpropylphosphine oxidediethyldodecylphosphine oxide diethyltetradecylphosphine oxidedipropyldodecylphosphine oxide bis- (hydroxymethyl) dodecylphosphineoxide bis- (2-hydroxyethyl dodecylphosphine oxide(2-hydroxypropyl)methyltetradecylphosphine oxide dimethyloleylphosphineoxide, and

dimethyl- (Z-hydroxydodecyl) pho sphine oxide and the correspondingdecyl, hexadecyl, and octadecyl homologs of the above compounds.

Specific examples of nonionic detergents include nonyl phenol condensedwith either about 10 or about 30 moles of ethylene oxide per mole ofphenol and the condensation products of coconut alcohol with an averageof either about 5.5 or about 15 moles of ethylene oxide per mole ofalcohol and the condensation product of about 15 moles of ethylene oxidewith one mole of tridecanol.

Other examples include the Well known detergents sold under thetradename Pluronic which are prepared by condensing propylene glycolwith propylene oxide to form a hydrophobic base and then condensing saidhydrophobic base with ethylene oxide, the hydrophobic base having amolecular weight of from about 1500 to about 1800 and the total moleculehaving a molecular weight of, e.g., 2000, 3000, and 8000.

Another group of suitable nonionic detergents are sold under thetradename of Tetronic. These are prepared by condensing ethylene diaminewith propylene oxide to form a hydrophobic group (molecular weight-fromabout 2500 to about 3000) and condensing this hydrophobic group withethylene oxide to give a molecular weight of from about 5000 to 11,000.

Other examples include dodecyl phenol condensed with 12 moles ofethylene oxide per mole of phenol; dinonylphenol condensed with 15 molesof ethylene oxide per mole of phenol; dodecyl mercaptan condensed with10 moles of ethylene oxide per mole of mercaptan; bis(N-Z-hydroxyethyl)lauramide; nonyl phenol condensed with 20 moles ofethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with10 moles of ethylene oxide per mole of myristyl alcohol; lauramidecondensed with 15 moles of ethylene oxide per mole of lauramide; anddi-iso-octylphenol condensed with 30 moles of ethylene oxide per mole ofdi-iso-octylphenol.

Specific examples of sulfoxide detergents include:

The liquid detergent compositions of this invention contain from about1% to about 40% by weight of the composition of the detergentshereinbefore described. The minimum amount is set by practical productconsiderations of detergency benefits derived per unit volume. The upperlimit, on the other hand, is set by several considerations includingviscosity, crystalline solubility, and the possibility of forming liquidmesomorphic phases or an insolubilizible, immiscible second isotropicphase.

Although it is not desired to be bound by theory it is believed thatcertain electrolytes having an anion with relatively low charge density(ratio of number of charges in the anion to volume of the anion) aremost effective in preventing separation of a second immiscible isotropicliquid phase. The effective anions are singly charged. Therefore, theanions with large volumes are effective.

R groups which fit the definition hereinbefore given are unsaturatedaliphatic radicals containing from about 2 to about 7 carbon atoms andwherein there is unsaturation selected from the group consisting of onethree covalent bond linkage and from one to two two covalent bondlinkages; phenyl radicals; naphthyl radicals, substituted phenylradicals containing from one to three substituents selected from thegroup consisting of methyl, ethyl, propyl, isopropyl, pentyl, isopentyl,butyl, isobutyl, chloro, fluoro and nitro groups and mixtures thereof;naphthyl radicals containing from one to about three substituentsselected from the group consisting of chloro, fluoro, and nitro groupsand mixtures thereof; phenyl alkyl radicals wherein the above phenylradicals, including substituted phenyl radicals, are attached toalkylene radicals selected from the group consisting of ethylene,propylene, butylene, pentylene and hexylene groups; branched chainsaturated aliphatic radicals containing from about three to about sixcarbon atoms; saturated aliphatic radicals containing from one to aboutfive carbon atoms and containing from one to about five chlorine atoms;unsaturated aliphatic radicals containing from two to about five carbonatoms wherein there are from zero to one three covalent bond linkages,from zero to two two covalent bond linkages and containing from one toabout five chlorine atoms; and mixtures thereof.

Specific R groups fitting the definition hereinbefore given includephenyl, benzyl, naphthyl, methylphenyl, dimethylphenyl, ethylphenyl,diethylphenyl, propylphenyl, dipropylphenyl, isopropylphenyl,butylphenyl, isobutylphenyl, 3-phenylpropyl, 2-phenylethyl, methybenzyl,nitrophenyl, dinitrophenyl, chlorophenyl, methylchlorophenyl,ethylfluorophenyl, chloronaphthyl, dichloronaphthyl, nitronaphthyl,dinitronaphthyl, isopropyl, isobutyl, chloroethyl, chloropropyl,chloroisobutyl, 1,2-dichloro-Z-pentene, 4,4-dichloro-2-butene,1-chloro-3-pentene, and chloromethylbenzyl.

Examples of electrolytes as generically defined above which areparticularly effective in solubilizing the detergent surfactants of thisinvention include the ammonium, monoethanolammonium, diethanolammonium,triethanolammonium, sodium, and potassium crotonates; sorbates;benzoates; o-nitrobenzoates; p-chlorobenzoates; phenylacetates;cinnamates; naphthoates; isobutyrates; isovalerates; trimethyl acetates;trichlonoacetates; ethylbenzene phosphonates; and furoates. Thesepreferred solubilizing agents are particularly effective in the presenceof these polyvalent electrolyte salts which are polyphosphate buildersalts such as tetrapotassium pyro-phosphate and polycarboxylate buildersalts such as sodium and potassium nitrilotriacetates andethylenediaminetetraacetates 5 and substituted methylene and ethylenediphosphonate: (e.g., trisodium ethane-l-hydroxy 1,1-diphosphonate).

These electrolytes are the solubilizing agents of this in vention; theyperform the solubilizing function wherea other electrolytes havinganions with relatively high charg. densities have generally the oppositeeffect, i.e., promott separation. Examples of electrolytes which tend tocaust a separation of a second isotropic liquid phase IHCllldt many ofthe common ingredients found in detergent com positions such as thepolyvalent electrolytes hereinbefori mentioned, e.g., potassium andsodium pyrophosphates sodium and potassium tripolyphosphates, potassiuman sodium silicates, potassium and sodium sulfates, potassiurr andsodium ethylenediamine tetraacetates, and sodiurr potassium nitrilotriacetates.

The solubilizing electrolytes of this invention are user in an amountfrom about 0.5% to about 20% by weigh of the liquid detergentcomposition and sufficient to pro vide a homogeneous composition.Preferably only suflicient solubilizing electrolyte is used to create ,asingle phase in the temperature range desired. It will be understoodthat all compositions coming within the scope of the ranges 01components disclosed which are not homogeneous by reason of a secondimmiscible isotropic liquid phase, are benefited by the presence of asolubilizing electrolyte tc aid in reducing the area of the secondisotropic liquid phase on the appropriate phase diagram (e.g., as inFIG. 2) at a given temperature and increasing the area of the firstisotropic liquid phase which has the practical efiect of changing moreof the second isotropic liquid into the first isotropic liquid phase.(It is believed that this result is effected by a raising of the minimumtemperature at which said second isotropic liquid can exist with aconcomitant reduction in the area occupied by the second isotropicliquid at a given temperature.) It will be further understood that wherethe sole separating phase is one which is not affected by the action ofthe solubilizing electrolyte, e.g., where the sole separating phase iscrystalline inorganic builder, there is no benefit from using asolubilizing electrolyte. These solubilizing electrolytes can be used incombination with other solubilizing agents and solvents which solubilizeother separating phases as Well as the second liquid phase.

With reference to FIGURES 2 and 3, the effect of the solubilizingelectrolytes can be explained readily. The area in each figure definedby the axes and the boundary line is the single (first) isotropic liquidphase region. When a conventional detergent builder or other polyvalentelectrolyte is added to aqueous solutions of the detergents utilized inthe compositions of this invention (FIGURE 2), the amount of detergentwhich can be placed in a single homogeneous liquid phase (firstisotropic liquid phase) is increased initially because the solubility ofthe first mesomorphic phase (middle) is initially increased. When theseparating mesomorphic phase is neat, an increase in the amount ofbuilder electrolyte decreases the amount of detergent and builder whichcan be placed in a single homogeneous liquid phase. A second immiscibleisotropic liquid (lye) separates as the conventional and highlydesirable high electrolyte/ surfactant ratios and it is this phase whichnormally prevents the formation of a homogeneous liquid composition.

Use of a solubilizing electrolyte in a water-detergent system gives thephase relationship as shown in FIGURE 3. At high ratios of solubilizingelectrolyte to detergent the separating phase is electrolyte crystalsrather than a second liquid phase and the ,amount of electrolyte thatcan be present before phase separation occurs is much greater than withpolyvalent electrolytes alone. Addition of a solubilizing electrolyte toa composition containing builder electrolyte at a given temperaturemodifies the builder detergent phase diagram (e.g., FIGURE 2) to lookmore like FIGURE 3 and more builder can be placed in a homogeneouscomposition. As hereinbefore discussed, this is believed to occur byraising the minimum temperature at vhic-h the second isotropic liquidcan exist and thereby lecreasing the area, on a phase diagram, of thesecond sotropic liquid for a given temperature.

The presence of a second immiscible isotropic liquid )hase is also afunction of temperature. As the temperaure of the composition is raised,a second liquid phase eparates. For some detergents this separationoccurs only vhen a polyvalent electrolyte, e.g., builder, is present.The :olubilizing electrolytes raise the temperature at which hisseparation occurs. The presence of a temperature-de- )endent secondliquid phase which exists without a polylalent electrolyte being presentis a function of water iolubility and cannot readily be predicted. Ingeneral, with respect to the hydrophobic group, the longer chain lengths1Y6 less soluble and more prone to exhibit this phenome- 1011. Withrespect to the hydrophilic group, ethylene oxide condensates andphosphine oxide surfacants are more likely to exhibit this phenomenon,whereas amine oxide and sultaine surfactants generally do not. Theprimary bene- [it from the use of solubilizing electrolytes in a liquidcomposition of this invention is derived whenever a second liquid phaseis the separating phase.

Variation in degree of effectiveness is found in solubilizing thevarious surfactants with the various solubilizing electrolytes.

When used with the relatively water-insoluble sultaine detergentshereinbefore described, the electrolyte solubilizing agents of thisinvention are present in the liquid detergent composition in an amountfrom about 0.5% to about by weight of the liquid detergent compositionand sufficient to lower the Krafft temperature of the sultaine detergentin the liquid detergent composition below about 70 F. (roomtemperature), prefer-ably below 40 F., to prevent the crystallinedetergent from separating out of solution during normal use and storage.

These particularly relatively water-insoluble sultaine detergents areunique in that the addition of the electrolytes of this invention totheir aqueous solution lowers their Kraift temperature as hereinaftermore fully described. This Krafft temperature is really a narrow rangeof temperature for a given compound within which a small increase intemperature gives a very large increase in solubility of the crystallinesurfactant. Lowering of the Krafft temperature for a givensultaine-electrolytewater system has the practical effect of raising thecrystalline solubility of the surfactant in water for any temperaturewhich is above the temperature to which the Kralft temperature islowered and which is below the Krafft temperature of the surfactant inwater (without solubilizing electrolyte). Normally, the addition of anelectrolyte to an aqueous anionic surfactant solution will raise thisKrafft temperature (lowering practical solubility), but the addition ofthe electrolytes of this invention to the sultaine detergents utilizedin the compositions of this invention lowers their Krafft temperature(increases practical solubility).

The effect of this lowering of the Kratft temperature is such thathomogeneous liquid detergent formulations can be prepared containing aconsiderable amount of sultaine detergent by the use of solubilizingelectrolytes. To explain, the mechanism by which these particularelectrolytes solubilize these sultaine detergents, reference is made toa phase diagram typical of the liquid systems of this invention, FIG. 1,in which the crystalline solubility (to left of point A) of arepresentative sultaine detergent of this invention in Water is plottedas a function of temperature with a solid line (Tw is the Kraffttemperature of the sultaine detergent in water) and the crystallinesolubility (to the left of point A of the same representative sultainedetergent in an aqueous solubilizing-electrolyte solution of constantconcentration is plotted as a function of temperature with a broken line(T is the Krafft temperature of the sultaine detergent in electrolytesolution). It will be understood that the position of this broken linevaries with the concentration 8 of solubilizing-electrolyte in water andthat there is a series of these broken line curves for differentelectrolyte concentrations. Up to a certain limit, the more electrolytethat is present the lower the broken line curve is on the diagram.

The lines on the diagram represent the boundaries for homogeneoussolutions. Region B is homogeneous and is commonly referred to as nigre;regions C and C are characterized by the presence of liquid mesomorphicphase; regions D and D are characterized by the presence of anotherliquid mesomorphic phase; and region E is characterized by the presenceof crystals of detergent plus detergent solution.

When the addition of the solubilizing-electrolytes of this inventionlowers the Krafft temperature of the sultaine detergent, as hereinbeforedescribed, below the temperature of the liquid detergent composition,the crystalline solubility of the sultaine detergent in water issubstantially increased. The practical result is that a greater amountof the sultaine detergent can be used in the detergent composition whilemaintaining homogeneity. In general, the liquid compositions of thisinvention containing the relatively water-insoluble sultaines will be tothe left of A and A on the accompanying sultainewater phase diagram(FIG. 1). (A and A are the crystalline solubility points hereinbeforedescribed.) The amount of lowering of the Krafft temperature isdependent upon the amount and, particularly, the type of electrolytepresent as well as the molecular structure of the sultaine.

In addition to the detergents and solubilizing agents hereinbeforedescribed, the detergent compositions can also contain from 0% to about40% by weight of the composition of polyvalent electrolytes, but no morethan can be dissolved in the compositions. These polyvalent electrolytescan be inert salts, which are associated with the detergent materials,such as sodium sulfate or can be desirable detergent builderelectrolytes. Examples of water soluble inorganic alkaline detergencybuilder salts are alkali metal carbonates, phosphates, polyphosphates,and silicates. Specific examples of such salts are sodium and potassiumtripolyphosphates, carbonates, pyrophosphates, phosphates, andhexametaphosphates. Examples of organic alkaline sequestrant buildersalts are (1) alkali metal amino polycarboxylatcs [e.g., sodium andpotassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)- ethylenediamine triacetates, nitrilo triacetates, and N-(2-hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid(e.g., sodium and potassium phytates-see U.S. Patent 2,739,942); (3)water soluble ethane-1- hydroxy-1,1-diphosphonates (e.g., the trisodiumand tripotassium salts); (4) water soluble salts of methylenediphosphonic acid (e.g., trisodium and tripotassium methylenediphosphonate and the other salts described in the copending applicationof Francis L. Diehl, Ser. No. 266,025 now Patent No. 3,215,030, filedMar. 18, 1963); (5) water soluble salts of substituted methylenediphosphonic acids (e.g., trisodium and tripotassium ethylidene,isopropylidene, benzylmethylidene, and halomethylidene diphosphonatesand the other substituted methylene diphosphonates disclosed in thecopending application of Clarence H. Roy, Ser. No. 266,055, filed Mar.18, 1963); (6) water soluble salts of polycarboxylic polymers andcopolymers as described in the copending application of Francis L.Diehl, Ser. No. 269,359, filed Apr. 1, 1963 now Patent No. 3,308,067,Le, a polyelectrolyte builder material consisting of water-soluble saltsof a polymeric aliphatic polycarboxylic acid selected from the groupconsisting of (a) water soluble salt of a homopolymer of an aliphaticpolycarboxylic acid having the following empirical formula:

9 wherein X, Y, and Z are each selected from the group consisting ofhydrogen, methyl, carboxyl, and carboxymethyl,

at least one of X, Y, and Z being selected from the group consisting ofcarboxyl and carboxyrnethyl, provided that X and Y can be carboxymethylonly when Z is selected from carboxyl and carboxyrnethyl, wherein onlyone of X, Y, and Z can be methyl, and wherein n is a Whole integerhaving a value within a range, the lower limit of which is three and theupper limit of which is determined by the solubility characteristics inan aqueous system;

(b) a water-soluble salt of a copolymer of at least two of the monomericspecies having the empirical formula described in (a); and,

(c) a water-soluble salt of a copolymer of a member selected from thegroup of alkylenes and monocarboxylic acids with the aliphaticpolycarboxylic compounds described in (a), said copolymers having thegeneral formula:

H R Y COOH m wherein R is selected from the group consisting ofhydrogen,methyl, carboxyl, carboxymethyl, and carboxyethyl;

wherein only one R can be methyl; wherein m is at least 45 mole percentof the copolymer; wherein X, Y, and Z are each selected from the groupconsisting of hydrogen, methyl, carboxyl, and carboxymethyl,

at least one of X, Y, and Z being selected from the group of carboxyland carboxymethyl provided that X and Y can be carboxyrnethyl only whenZ is selected from carboxyl and carboxymethyl, wherein only one of X, Y,and Z can be methyl; and wherein n is a 1 about 80, calculated at theacid form (e.g., polymers of itaconic acid, aconitic acid; maleic acid;mesaconic acid; fumaric acid; methylene malonic acid; and citraconicacid and copolymers with themselves and other compatible monomers suchas ethylene); and (7) mixtures thereof.

Mixtures of any and all of the organic and/or inorganic builders can beused and are generally desirable. Especially preferred are the mixturesof builders disclosed in the copending application of Burton H. Gedge,Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodiumtripolyphosphate, sodium nitrilotriacetate, and sodiumethane-l-hydroxy-l,l-diphosphonate.

At high ratios of these polyvalent, e.g., builder electrolytes todetergents (as hereinbefore described and as illustrated in FIG. 2) asecond liquid tends to separate and it is this second liquid phase whichis most readily controlled by the solubilizing electrolytes of thisinvention as hereinbefore described.

Other ingredients can also be present in the liquid detergentcompositions of this invention without detracting from the advantageousproperties of the invention.

Anti-redeposition agents such as carboxymethylcel l-ulose and anionic,cationic or nonionic detergents can also be added. Typical minoradditives which can be present include suds boosters and suppressants,dyes, opacifiers, perfume, corrosion, inhibitors and anti-microbialagents.

All percentages, ratios and parts herein are by weight unless otherwisespecified.

The practice of this invention is demonstrated in the followingexamples.

' Example I Homogeneous aqueous liquid compositions were preanddiiferent solubilizing electrolytes, both with (Composi- SolubilizingElectrolyte Percent Percent Percent Percent Solubilizing Sultainesolubilizing Sultaine K4P O1 Electrolyte Detergent Electrolyte DetergentSodium crotonate- 7 27 5 30 Sodium acrylate 10 5 10 5 10 Sodium sorbate.8 30 6 16 32 Sodium benzoate 9 17 5 17 34 Sodium 3,5-dinitrobenzoate 824 9 4 8 Potassium o-mtrobenzoate 9 12 6 13 Potassium p-chlorobenzoate 816 7 12 23 Sodium phenyl acetate 7 32 6 15 Sodium oinnamatem 8 23 6 1325 Sodium napthoate. 8 24 8 7 14 Sodium isobutyrate 7 29 7 9 18 Sodiumisovalerate 9 10 6 14 28 Sodium trimethylacetate 9 10 6 14 28 Sodiumethylbenzene phosphonate 8 23 6 13 26 Sodium furoate 10 24 10 13 25 None0 0. 1 0 0. 1

1 Saturated.

whole integer within a range, the lower limit of which is three and theupper limit of which is determined primarily by the solubilitycharacteristics in an aqueous system; said polyelectrolyte buildermaterial having a minimum molecular Weight of 350 calculated as the 7,

acid form and an equivalent weight of about 50 to When in the aboveexample, any of the following detergent compounds, or mixtures of thefollowing compounds, are substituted for the specific sultainedetergent, either wholly or in part, substantially equivalent resultsare obtained in that significantly more of the sultaine detergentsand/or builder can be added to form a'homogeneous 1 1 solution than canbe added Without the solubilizing electrolytes being present: 3-(N,N-dimethyl-N-hexadecylammonio) -propane-1- sulfonate,

droxymethyl)octadecylamine oxide, bis(3-hydroxypropyl) pentadecylamineoxide, bis(2-hydroxypropyl)heptadecylamine oxide, bis(ethyl)eicosylamine oxide, bis(2,3-dihydroxypropyl)decylamine oxide,bis(propyl)oleylamine 2-(N,N-dihydrogen-N-dodecylammonio)-ethane-1- g gl ff gl z h ri FZ fZIiI Q sulfonate, g c mp un s w erein one o e wos o ay ams 4-(N,N-diethyl-N-tetradecylammonio)-2-hydroxybutaneare f z g d gfi 3 13 3 g methyl, P Lsmionate, p py 1 y e p py Y rp -py. y s4-(N,N-diethyl-N-eicosylammonio)-butane-1-sulf0nate, methyl, and y rXypropy1 groups; the corresponding3-(N-methyl-N-ethyl-N-octadecylammonio)-2-hydroxy- Compounds WheremZ'hYdTOXY3'decoxypmpyl, Y' propane l sulfonate, droxydodecyl,2-hydroxy-3-octadecoxypropyl, decyl, tetra-4-(Nhydrogen-N-rnethyl-N-decylammonio)-3-hydro decyl, Z-decoxypropyl,Z-tetradecoxyethyl, Z-(Z-decoxy- .butane l sulfonate, ethoxy )ethyl,pentadecyl, octadecyl, heptadecyl, eicosyl,2-(N-hydr0gen-N-ethyl-N-oleylammonio)-ethane-loleyl, llnolcyl, hnolenyl,-P PY yL p py and sulfonate; tetrabutyl groups are substituted for thelong chain group. h N h Similarly, when in the above examples any of thefolthe g g g i W g? 3 g? group? lowing compounds, or mixtures thereof,are substituted i? i lsmute or i y g for the specifically nameddetergents, either wholly or in f f 3 sltute or g i E part,substantially equivalent results are obtained in that y groups y rogensare Su sum or more of the detergents and builders are formed into amethgl i F g i g g z i i z homogeneous solution than are formed when thesolubi- Poun l erem ecy O ecy Ia eXa ecy octa' lizing electrolytes arenot present: octadecyl methyl sulfdecyl, eicosyl, oleyl, linoleyl,linolenyl, 4-pr py oxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxygiyi g i fi i g g h i ig g tridecyl methyl sulfoxide,3-hydroxy-4-dodecoxybutyl are su S e or e Ong y c ams m e a CV methylsulfoxide, Z-hydroxypentadecyl methyl sulfoxide; compoun s. E am 1e thecorresponding compounds wherein decyl, undecyl, x p dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecy-l, hepta- Homogeneous aqueous liquidcompositions were predecyl, octadecyl, eicosyl, tetrapropylene,2*(2-dodecoxypared containing varying amounts of the sultaine detergentethoxy) ethyl, 2-methoxypentadecyl, 3-ethoxyundecyl, of Example I incombination with polycarboxylate deterand 3-hydroxy-4-decoxybutyl groupsare substituted for gency builders and various electrolyte solubilizingagents. the long chain groups. All percentages are by weight. Thefigures represent the E I IV maximum amounts of sultaine detergent andbuilders xamp e which can be solubilized by the respective electrolytes.Homogeneous aqueous liquid compositions were pre- Solubilizing PercentPercent Electrolyte Solubilizing Builder Builder Sultaine ElectrolyteDetergent None i. Trisodium nitrilo triacetate Saturatedsoluti0n 1Sodium isovalerate..- do 13 Sodium cinnamate 6 do 15 10 NoneTetrapotassium ethylenediarm'ne- Saturated soluti0n 1 tetraacetate.Sodium crotonate 13 do 32 21 Example 111 Homogeneous aqueous liquidcompositions were prepared containing varying amounts of dodecyldimethyl amine oxide detergent in combination with potassiumpyrophosphate builder (13), tetrasodium ethylenediaminetetraacetatebuilder (4-5) and sodium nitrilo triacetate builder (68); Allpercentages are by Weight. The figures represent the maximum amounts ofamine oxide and builders which can be solubilized by the respectiveelectrolytes.

Percent Percent Percent Solubilizing Electrolyte Solubilizing AmineBuilder Electrolyte Oxide (l) None 9 14 (2) c. Potassium sorbate. 9 1623 (3) Sodium napthoate. 8 14 20 (4), None 12 24 (5) Potassium benzoate11 18 36 (6)," None 15 30 (7) Sodium phenylacetate. 10 17 34 (8) Sodiumtrimethyl acetate- 10 17 25 When, in the above examples any of thefollowing compounds, or mixtures thereof, are substituted for thespecifically named detergents, substantially equivalent results areachieved in that more of the detergents and builders can be added toform a homogeneous solution than can be added without the solubilizingelectrolytes being present: bis(2-hydroxyethyl)tetradecylamine oxide,bis(hypared containing varying amounts of dimethyldodecylphosphine oxidedetergent and potassium pyrophosphate builder (1-3), sodiumnitrilotriacetate builder (4-5) and potassium ethylenediaminetetraaceticbuilder (6-10) in ratios of builder to detergent of approximately 2:1.All percentages are by weight and the figures represent the maximumamounts of phosphine oxide and builders which can be solubilized by therespective electrolytes.

When any of the following compounds, or mixtures thereof, aresubstituted, either wholly or in part for the specifically nameddetergents in the above examples, substantially equivalent results areobtained in that more de- 13 tergents and builders are solubilized withthe solubilizing electrolytes than without:

dimethyltetradecylphosphine oxide; diethyldecylphosphine oxide;bis-(Z-hydroxyethyl)hexadecylphosphine oxide; dihydroxymethylpentadecylphosphine oxide; dipropylundecylphosphine oxide;bis-(Z-hydroxypropyl)tetrapropylene phosphine oxide;bis-(3-hydroxypropyl)oleylphosphine oxide;

the corresponding compounds in which methyl, ethyl, 2- hydroxyethyl,hydroxy methyl, propyl, 2-hydroxypropyl and 3-hydroxypropy-l groups aresubstituted for one of the short chain groups in the above compounds;the corresponding compounds in which decyl, undecyl, dodecyl,tetradecyl, pentadecyl, tridecyl, hexadecyl, heptadecyl, octadecyl,eicosyl, tetrapropylene, diheptene, o-leyl, linoleyl, and linolenylgroups are substituted for the long chain group in each of the abovecompounds.

Example V Homogeneous aqueous liquid compositions were prepared withnonionic detergent (nonylphenol polyethoxy ethanol with an average ofabout 10 ethoxy groups) and potassium pyrophosphate builder (1-3),sodium nitrilotriacetate builder (45), and potassium ethylenediaminetetraacetate builder (6-8) as builders.

Percent Percent Percent Solubilizing Electrolyte Solubilizing DetergentBuilder Electrolyte (1) None 9 (2). Sodium crotonste 5 5 9 (3 Sodiumbenzoate 8 8 16 5 10 10 20 I 7 14 (7)..- Sotditum trimethylaee- 16 16 32a e. (8).-- Sodium erotonate 11 11 21 2,6-dimethyldodecanol,6-hexyldecanol, 8-butylhexadec anol, and Z-butenyl-Z-octanol; (2)tetrapropylenephenol, octylphenol, decylphenol, tridecylphenol,diheptenephenol, octadecylphenol, dioctylphenol, dinonylphenol,3-hexylheptylphenol, pentadecylphenol, tetradecylphenol, dodecylphenol,and diisoootylphenol; (3) myristamide, stearamide, palrnitamide,oleamide, linoleamide, linolenamide,

and capro-amide; and (4) decyl mercaptan, dodecyl mercaptan,tert-dodecyl mercaptan, tetrapropylene mercaptan, oleyl mercaptan,linoleyl mercaptan, linolenyl mercaptan, eicosyl mercaptan, pentadecylmercaptan, tridecyl mercaptan, heptadecyl mercaptan, andZ-butenyl-Z-octyl mercaptan with ten, fifteen, twenty,-and twenty-fivemoles respectively of ethylene oxide; nonionic detergents prepared bycondensing the aforementioned alcohols wit-h three, I

- amine wit-h twenty, thirty, forty and fifty moles of pro-pylene oxideand thereafter condensing the resulting products with thirty, forty andfifty moles respectively of ethylene oxide; nonionic detergents preparedby condensing propylene glycol with twenty-five, thirty and thirty-fivemoles 1 respectively of propylene oxide and thereafter condensing theresulting products with twenty, thirty, forty, and

fifty moles respectively of ethylene oxide.

14 Example VI An aqueous homogeneous liquid detergent composition wasprepared with the following formula in which all percentages are byweight of the composition.

The composition was adjusted to Na:K ratio of 65:35 by the addition ofNaOI-I and KOH and the pH of the composition was 12.5. Without thesodium benzoate the composition was not homogeneous.

Example VII When in the previous examples any of the followingsolubilizer compounds, or mixtures thereof, are substituted, eitherwholly or in part, for the specifically named solubilizing electrolytes,substantially equivalent results are obtained in that more of thedetergents and builders can be formed into homogeneous solutions withthe solubilizing electrolytes than without: crotonates, sorbates,benzoates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates,cinnamates, naphthoates, chloronaphthoates, fluoronaphthoates,nitronaphthoates, trichloronaphthoates, chlorodinitronaphthoates,chlorofluoron-aphthoates, isobutyrates, isovalerates, trimethylacetates,ethylbenzene phosphonates, furoates, ,B-chloro propiolates, propiolates,a-chloro acrylates, B-chloro acrylates, acrylates, pentyl benzoates,isopentyl benzoates, butyl benzoates, isobutyl benzoates, propylbenzoates, isopropyl benzoates, ethyl benzoates, methylethyl benzoates,trimethyl benzoates, diisopropyl benzoates, chloromethyl benzoates,methylnitro benzoates, fluoro benzoates, methyl benzoates, 3-phenylpropionates, 2-phenylbutyrates, 4-phenylbutyrates, 5-chloro-l-carboxylate-pentaues, 6-nitrophenyl-l-carboxylate hexanes,mandelates, trichloroacetates, 0c chloro 'butyrates, dimethylbenzoates,and mixtures of any of these Example VIII When in the previous examplesany of the following polyvalent electrolytes, or mixtures thereof aresubstituted, either wholly or in part, for the specifically namedpolyvalent electrolytes, substantially equivalent results are obtainedin that more of the detergents and builders can be formed intohomogeneous solutions with the solubilizing electrolytes than without:tripolyphosphates; sulfates; carbonates; pyrophosphates; phosphates;hexamethaphosphates; ethylenediaminetetraacetates; N-(2-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N (2hydroxyethyl) nitrilodiacetates; phytates;ethane-l-hydroxy-l,l-diphosphonates; methylane diphosphonates; andethylidene, isopropylidene, benzylmethylidene and chloromethylidenediphosphonates; salts of polymers of itaconic acid, aconitic acid,maleic acid, mesaconic acid, fumaric acid, methylene malonic acid andcitraconic acid and copolymers with themselves and/or ethylene and/ oracrylic acid in e.g. 1:1 molar ratios and having molecular weights of75,000; 100,000; and 125,000 (the copolymers with ethylene and/oracrylic acid having equivalent weights, based on the acid form of 65, 70and 75) in the form of their sodium, potassium, triethanolammonium,diethanolammonium, and monoethanolammonium salts.

What is claimed is:

I claim:

1. An aqueous homogeneous liquid detergent composition consistingessentially of:

(I) from about 1% to about 40% by weight of the 15 composition of adetergent selected from the group consisting of (A) A detergent havingthe formula R2 wherein R and R are each selected from the groupconsisting of hydrogen, methyl, and ethyl groups, R is a straight chainalkylene group containing two to four carbon atoms, and having from toone hydroxyl group substituted on a secondary carbon atom, and R is analkyl chain of from about 10 to about 20 carbon atoms;

(B) A detergent having the formula R R R N O wherein R is selected fromthe group consisting of alkyl, alkyl monohydroxy, and alkoxymonohydroxypropyl radicals wherein the alkyl and alkoxy portions of saidradicals contain from about to about carbon atoms and R and R are eachselected from the group consisting of alkyl radicals and allranolradicals containing from one to about three carbon atoms;

(C) A detergent having the formula R' R R P O wherein R is selected fromthe group consisting of alkyl and alkyl monohydroxy radicals containingfrom about 8 to about 16 carbon atoms and R and R are each selected fromthe group consisting of alkyl radicals and alkanol radicals containingfrom one to about three carbon atoms;

(D) Nonionic detergents having the formula R (C H O) H wherein Rrepresents a hydrophobic base selected from the group consisting of (1)alkoxy groups containing from about 8 to about 20 carbon atoms, (2)alkyl phenoxy groups wherein the alkyl group contains from about 6 toabout 18 carbon atoms, (3) condensation products of propylene glycol andpropylene oxide with a molecular weight of from about 1500 to about1800, (4) fatty amides containing from about 10 to about 20 carbonatoms, (5) higher alkyl mercaptans containing from about 10 to about 20carbon atoms, (6) condensation products of propylene oxide and ethylenediamine constituting from about 20% to about 60% by Weight of thefinished nonionic detergent molecule and (7) condensation products offatty alcohols containing from about 10 to about 20 carbon atoms andfrom about three to about 8 propylene oxide units and wherein x is aninteger from about 4 to about for (1), (2), (4), and (5), but not lessthan about 0.4 of the number of carbon atoms in the hydrophobic group,and sufiiciently large to give the detergent a molecular Weight of fromabout 2,000 to about 10,000 for (3); of from about 5,000 to about 11,000for (6); and of from about 750 to about 1800 for (7), and wherein y isan integer equal to the number of ethylene oxide chains;

(E) A detergent having the formula 0 R iiCH wherein R is an alkylradical containing from about 10 to about 20 carbon atoms and containsfrom 0 to 1 hydroxyl snbstituents and from 0 to five ether linkages;

(F) and mixtures thereof;

(11) From 0% to about by weight of the composition of a polyvalentelectrolyte salt selected from the group consisting of a polyvalentelectrolyte salt selected from the group consisting of (1) sulfates; (2)carbonates; (3) tripolyphosphates; (4) pyrophosphates; (5)orthophosphates; (6) hexametamula:

1 it (JOOH 11 wherein X, Y, and Z are each selected from the groupconsisting of hydrogen, methyl, carboxyl, and carboxymethyl,

at least one of X, Y, and Z being selected from the group consisting ofcarboxyl and carboxymethyl, provided that X and Y can be carboxymethylonly when Z is selected from carboxyl and carboxymethyl, wherein onlyone of X, Y, and Z can be methyl, and wherein n is a whole integerhaving a value within a range, the lower limit of which is three and theupper limit of which is determined by the solubility charac teristics inan aqueous system; (b) a watersoluble salt of copolymer of at least twoof the monomeric species having the emperical, formula described in (a);and (c) a water-soluble salt of a copolymer of a member selected fromthe group of alkylenes and monocarboxylic acids with the aliphaticpolycarboxylic compounds described in (a), said copolymers having thegeneral formula:

i t i H R i-m Y DOOH m n wherein R is selected from the group consistingof hydrogen,

methyl,

carboxyl, carboxymethyl, and carboxyethyl;

wherein only one R can be methyl; wherein m is at least 45 mole percentof the copolymer;

wherein X, Y, and Z are each selected from the group consisting ofhydrogen, methyl, carboxyl, and carboxymethyl,

at least one of X, Y, and Z being selected from the group of carboxyland carboxymethyl provided that X and Y can be carboxymethyl only when Zis selected from carboxyl and carboxymethyl, wherein only one of X, Yand Z can be methyl; and

wherein n is a whole integer within a range, the lower limit of which isthree and the upper limit of which is determined primarily by thesolubility characteristics in an aqueous system; said polyelectrolytebuilder material having a minimum molecular weight of 350 calculated asthe acid form and an equivalent weight of about 50 to about 80,calculated as the acd form; and (19) mixtures thereof, the cations ofthe above polyvalent electrolytes being selected from the groupconsisting of sodium, potassium, ammonium; triethanol ammonium,diethanol ammonium and monoethanol ammonium cations and mixturesthereof;

(III) From about 0.5% to about 20% by weight of the composition, andsufficient to keep the composition homogeneous, of solubilizingelectrolytes selected from the group consisting of compounds having theformula wherein M is a cation selected from the group consisting ofsodium, potassium, triethanolammonium, diethanolammonium, andmonoehtanolammonium cations, and mixtures thereof, and R is selectedfrom the group consisting of unsaturated aliphatic radicals containingfrom 2 to about 7 carbon atoms; aromatic, substituted aromatic, andaromatic alkyl radicals containing from 6 to about 12 carbon atomsselected from the group consisting of phenyl radicals, naphthylradicals, substituted phenyl radicals containing from one to threesubstituents selected from the group consisting of methyl, ethyl,propyl, isopropyl, peutyl, isopentyl, butyl, isobutyl, chloro, fluoro,and nitro groups and mixtures thereof, napthyl radicals containing fromone to about three substituents selected from the group consisting ofchloro, fluoro, and nitro groups and mixtures theerof; and phenyl alkylradicals wherein the above phenyl radicals are attached to alkyleneradicals selected from the group consisting of ethylene, propylene,butylene, pentylene, and hexylene groups; branched chain saturatedaliphatic radicals containing from three to about six carbon atoms;chloro-substituted saturated and unsaturated aliphatic radicalscontaining from one to about carbon atoms; sodium, potassium,triethanolammonium, diethanolammonium, and monoethanolammoniumtrimethylacetates; sodium, potassium, triethanolammonium,diethanolammonium, and monoethanol ammonium ethyl benzene phosphates;sodium, potassium, triethanolammonium, diethanolammonium andmonoethanolammonium furoates; and mixtures thereof; and

(IV) The balance substantially water.

2. The composition of claim 1 wherein the detergent comprises a compoundhaving the formula R R R N O wherein R is selected from the groupconsisting of alkyl, alkylmonohydroxy, and alkoxy monohydroxypropylradicals wherein the alkyl and alkoxy contain from about to about 20carbon atoms and R and R are each selected from the group consisting ofalkyl radicals and alkanol radicals containing from one to about threecarbon atoms.

3. The composition of claim 1 wherein the detergent comprises a surfaceactive agent having the formula R' R R P- O wherein R is selected fromthe group consisting of alkyl and alkyl monohydroxy radicals containingfrom about 8 to about 16 carbon atoms and R and R are each selected fromthe group consisting of alkyl radicals and alkanol radicals containingfrom one to about three carbon atoms.

18 4. The composition of claim 1 wherein the detergent comprises acompound having the formula 0 R -g-om wherein R is an alkyl radicalcontaining from about 10 to about 20 carbon atoms and contains from O to1 hydroxyl substituents, and from 0 to five ether linkages.

5. The composition of claim 1 wherein the solubilizing electrolyte isselected from the group consisting of crotonates, sorbates,unsubstituted, benzoates, o-nitrobenzoates, p-chlorobenzoates,phenylacetates, cinnamates, naphthoates, isobutyrates, isovalerates,trimethyl acetates, trichloro acetates, ethylbenzene phosphonates,furoates and mixtures thereof.

6. The combination of claim 1 wherein the solubilizing electrolyte is abenzoate.

7. The composition of claim 1 wherein the solubilizing electrolyte is atrimethyl acetate.

8. The composition of claim 2 wherein the solubilizing electrolyte is asorbate and the polyvalent electrolyte is tetrapotassium pyrophosphate.

9. The composition of claim 3 wherein the solubilizing electrolyte is abenzoate.

10. The composition of claim 1 wherein the detergent has the formula 31RI I R SOa and wherein R and R are each selected from the groupconsisting of hydrogen, methyl and ethyl groups, R is selected from thegroup consisting of an alkylene group containing from two to four carbonatoms and an alkylene group of three carbon atoms with a hydroxyl groupsubstituted on the middle carbon atom, and R is an alkyl chain of (A)from about 12 to about 18 carbon atoms when R and R are hydrogens, (B)from about 16 to about 20 carbon atoms when R and R are each selectedfrom the group consisting of methyl and ethyl groups and R is anunsubstituted alkylene group as hereinbefore described, and (C) fromabout 14 to about 18 carbon atoms when R and R are selected from thegroup consisting of methyl and ethyl groups and R is a three-carbon atomalkylene group with a hydroxyl group substituted on the middle carbonatom, as hereinbefore described.

11. The composition of claim 1 wherein the solubilizing electrolyte isselected from the group consisting of crotonates, o-nitrobenzoates,p-chlorobenzoates, phenylacetates, cinnamates, naphthoates,isobutyrates, isovalerates, trimethylacetate, trichloroacetates,ethylbenzene phosphonates, furoates and mixtures thereof.

References Cited UNITED STATES PATENTS 2,441,341 5/1948 Vitalis 252363.5X 2,768,143 10/1956 Henry 252363.5 2,787,595 4/1957 Webb 2521383,001,945 9/1961 Drew et a1. 252l52 3,086,943 4/1963 Lang et al. 252l523,159,581 12/1964 Diehl 252l52 3,213,030 10/1965 Diehl 252l52 FOREIGNPATENTS 1,219,570 5/ 1960 France.

LEON D. ROSDOL, Primary Examiner.

SAMUEL H. BLECH, Examiner.

S. E. DARDEN, Assistant Examiner.

1. AN AQUEOUS HOMOGENEOUS LIQUID DETERGENT COMPOSITION CONSISTINGESSENTIALLY OF: (I) FROM ABOUT 1% TO ABOUT 40% BY WEIGHT OF THECOMPOSITION OF A DETERGENT SELECTED FROM THE GROUP CONSISTING OF (A) ADETERGENT HAVING THE FORMULA